Nitrogen-fixing blast fuenace



R. FRANCHOT 2,365,868

Filed Aug. 3, 1942 3 Sheets-Sheet l W NW. WW m m IUN x mm W. M. k 3 m 7 NW 9N W r V @N N O 9 MHAHOM l 1 NR w WW v w l. v wmxmzu view Bu WM k|| mvw EXREW I w R QN lll MN Q NIWN 0 UN fivm mm R I Wm wwmmh HHO mm Wm Dec. 26, 1944.

NITROGEN FIXING BLAST FURNACE Dec. 26, 1944. R. FRANCHOT NITROGEN FIXING BLAST FURNACE Filed A 3, 194g 3 Sheets-Sheet 2 MHz/04w Mam NW EEEW N a W W m w m UVUVUUV MV UUV MUV WW 01 1115 41111!!! 1' Mi li tilllnla R. FRANCHOT NITROGEN-FIXING BLAST FURNACE Dec. 26, 1944.

5 Sheets-Sheet 5 Filed Aug. 3, 1942 Richard; Franck/qt Eerrm Nitrogen: G W

a corporation of the:

lahingtomlMG; 'intolfflolumllia- Application August a me, Serial on. career 17 Claims lol. arc-1o) This invention relates to fixing; blast furnaces; and it comprises a. metallurgical blast furnace for producing iron and various. ferroalloys wherein a hearth-bush secfiorl of a usualor conventional oi structure provided plural air tuwres for introducing under substantial positive pressure jets orblasts of preheated e of gas firom bo'sh to shaft, the shalt hawiug the usual charging means at the remote end with pressure gas outlet means -and the hot gas outlet bein connected, adwantae geously through cog and cleaning means to a heat inte for preheating the air or the coke burned y preheated r ism supply heat to the hearth; the ore red asecondaryorasvlohnsonexpressedit, the composition ofthe top gas is an effect rather than a cause. It is now quite that the burdehratiooioretocokefl mtisgthecokecomsumptioru per unit of iron is determined by comditionsexistinginthehearth thezoneofhiehest temperature in the furnace. It is evident therefore that the Bell theory failed to account the second law or thermodynamica A. fact of blast practice which has not heretofore been generally reco is that the heat generated by coke combustion in the is; in great excess over the amount of heat that canbeusedinthesmeltingprocess. 'l'hisexcess is often over lull per and accounts for solution loss which is responsible for more than. half of the carbon monoxide gas produced. It can be truly stated that excess heat generated in the is largely responsible for the mm by er thereto or sensible heat from the I form of carbon monoxide in the top gas; the ratio of C0 to C02 being seldom under 2:1. In other words, over two of the coke carbon is converted to C0 in the smeltin process and; thus some 50 per cent of the fuel value remains in the gas. Usually the furnace functions. more emciently as a. gas producer than as an iron smelter.

A quite generally held theory purporting toaccolmt for the gas producing function of the blast furnace was first uttered by Lowthian Befl (Chemical Phenomena of Iron smelting-1872, D. Van Nostrand, New York). theory is based upon static equilibrium relations in the reduction of iron oxides by carbon monoxide forming 00:. The theory assumes that theprimary function. of the coke burning with blast oxygen to CO at the tuyeres is to provide a great excess of reducing gas needed to reduce the ore to metal.

gas producing fimction. The excess heat is or course carried into the by the gas produced imthehearth and incfiectmakestheiurnacea gas producer.

In this connection it has been more discovered that the alkali cyauides in the furserved concentrations of KCN vap r in the hearth gases, associated with potash accmnulation, are suificient to account for as much as 40 per cent oi the hearth heat" available at the high temperature at the tuyre leech-hearth heat being defined as the sum of the heat of CO formation plus the blast heat, and the sensible heat of carbon at the hearth temperature minu the sensible heat of the producer gas consistingot Thi theory has been regarded bymany as'full' explanation of the low of the blast furnace in metallizin iron ore.

Johnson (Principles, Operation and Products of the Blast Furnace. 1918, McGraw Hill, New York) has pointed out that the foregoing theory formCO andH-z Thebeneficialefiectuponfur mace economy of drying the blast is well In. a copcnding application Serial No. 428,770, filed January 29, 1942, I have described and was erroneous and showed that, the main funcclaimed ameans for improving the melting emciency of the blast furnace by reducing the accumulation of potash, thus releasing hearth heat otherwise utilized in cyanide vapor formation and by using the released heat-to increase the burden ratio of ore to coke. The described apparatus effects removal of cyanide vapor through throttled outlets in extremely small fractions of thefurnace gas carrying large fractions of the potash going. into the furnace in ore and coke.

The potash input is thus afforded a third outlet from the furnace in addition to those' afforded by the slag and the top gas.

In the present invention advantage is taken of the discovery that the chemical activity of the blast nitrogen in forming cyanide vapor in the hearth is responsible for large proportions of the coke consumed in metallizing iron ores in the blast furnace. The proportion of coke consumed in fixing blast nitrogen is, as I have found, as much as 50 per cent or more. it is an object of this invention to provide means whereby thefixation of blast nitrogen as cyanide can be fully controlled and the furnace can function to fix blast .nitrogen with recovery of cyanide and of reduced metal in desired Proportions. In shortjthe present invention comprises a nitrogen fixing blast furnace adapted to recover the nitrogen fixed and which now goes to waste. 1

In the prior art unsuccessful attempts have denser i0.

been ,made to recover cyanide formed in the blast furnace. In accordance with the present invention the blast furnace is adapted in structure to recover cyanide and thus to function as means for producing reduced metals and fixed nitrogen as byproducts.

This application is a continuation inpart of a prior and copending application Serial No. 387,

487, filed April 8, 1941, which is'adivisionof application Serial No. 262,717, filed March 18,

1939, now Patent No. 2,261,516, granted Novem her 4, 1941. J

In the accompanying drawings are shown, more or 'less diagrammatically, blast furnace structures with accessories illustrating the inyention and adapted to function in the described manner. In this showing,

Fig. 1 is a sectional view in elevation of a nitrogen fixing blast furnace adapted to recover substantial proportions of cyanide formed by m fixation of blast nitrogen; P

Fig. 2 is a similar view of a furnace of modified structure functioning like the furnace of Fig. 1,.

and v Fig. 3 is a similar view of a further modification of the furnace structure and accessories.

Referring to Fig. 1, a blast furnace hearth and bosh I of usual construction is provided with a top cover or roof 2 of refractory material such as flrebrick. The hearth has air tuyeres I sup- 00 plied with preheated air from a surrounding bustle pipe 4 provided with suitableqconnecting members. A metal outlet 5 and slag outlet 8 are shown. A hot gas outlet I runs through the roof 2. A gas conduit 8 lined with refractory insulated material conveyshot gases from the hot gas outlet I to a condenser I. adapted to condense cyanide vapor and to co'lllect liquid cyanide as condensed from the hot gases. Ad-

vantageously a refractory nozzle member 9 ter- 10 'minates the conduit 8 and'restricts the flow of gases through outlet 1, maintaining a relatively high gas pressure in the furnace.

As shown, condenser I0 is provided with a bell and hopper II for charging carbon and s da 0 Accordingly 0 instance, sodium carbonate, or sodium formatel in admixture into the condenserto serve as endothermic cooling agentsfor the hot gas, aiding in condensation of cyanide vapor to the molten or liquid form. The condenser-has a manhole Illa near the bottom. From the condenser in its lower portion, a gas conduit l2 leads toheat interchanger l3 which may be of a known metal or other suitable construction adapted to recuperate and, transfersensible heat from the gas to .the air blast blown by blower l4 through the interchanger or recuperator to air conduit l5 leading toair bustle pipe '4. From the interprovided with a valved inlet 22 for steam and water and a bottom solution outlet 23. A valved gas outlet is also provided near 'the top of the chamber for conductingammonia gas formed in hydrolysis of cyanide. A secondary tapping hole 25 is also shown in the bottom of the con- The' furnace shaft 21, communicates with the bosh and hearth through a shaft chute 28 which runs through the bosh roof 2. The shaft 21 is shown supported by pillars, although any-other convenient supporting .means may be employed.- At thetop of the shaft a hopper and bell 30 serve for charging fuel into the furnace. Near the'top of the shaft a gas outlet 3|, .controlled by valve 31 provides exit for gases passing from the furnace hearth up through the shaft. This gas outlet may run to a scrubber 33 where -condensable products-may be removedfrom the shaft gas to be collected as liquid in chamber 34. This chamber is shown provided with valved liq,- uid outlets l5 and 36 at diflerent levels and with 39, from which superheated steam may be run through pipe 40 to steam inlet ll in the lower part, of shaft 21. witha valved outlet .43 for carbonized material.

.In Fig. 2 is showna modified blast furnace having the hearthand bosh, hot gas outlet-and appurtenances similar to those shown in Fig.1. In the modified furnace, the shaft section comprises alhorizontally inclined rotary kiln i5 opl eratively connected (by gears) to rotating means' 46, such as a motor.

The kiln is adapted to discharge into shaft chute 20, which communicates with the furnace bosh through cover 2. The kiln has a gas'tight connection 41 at the lower end with chute 20, the

latter having a closed removable cover ll; At the upper end of-the kil ha vertical charging chamber 49 delivers into the kiln through a gas tight connection 50; The charging bell hopper 5i and the valved gas outlet conduit 52 are similar in function to those shown in Fig. l (30 and II).

Steam inlets-II, 54 are shown in chute?! which connects the horizontal furnace shaft to the bosh and hearth. 1 7 Fig. 3-shows a-fu'rther modification of the fur- 76 nace and accessories in' which the hearth-bosh gas outlet conduit' 31, having a valved branch 31a. -=The gas conduit is shown with a connection leading to boiler Stand steam'superheater The shaft may :be provided I greases section isrelatlvelwhlghandptowidedatits upper portion with a relatively thickened wall it. heavier wallmav be supported by piflars mailequatemnumhermdsnawdamundthe iurnacea. tuyres, metal and slag outlets are conventional and similar in function to those out Fig. l. and 2. Water" cooling plates idiortlwhoshwallaroshown hlgherhoshiscoveredhyarooimemherflwhich is built of rfifiractory brick and arched over the fresh. the hush cover Ell th outlet opencan formed to take gases vertically out oi the iuunace and refractory lined conduit iiileads gas flowing upwardly through the cover opening in a direction away from the furnace; This horizontal conduit ends a damned closure El. in the bottom or the conduit neartheilanged end, is placed a nozzle Ill, turning the flower gases downwarfly into condensing; chamber ll with a hell-shaped connectfon iiirhetween nozzle: and condenser." Chamber illsadapted to filter-and clean the gas and to recover condensed cyanide and similar matter.

it znap' contain adsorbent as filtering ma-- terial Ahove nozzle 58 a rod ll] is operated throuw a slinmng gland in the wad of conduit ill to clear the nozzle opening or obstruction Rod ll may carry refractory cone ll, servmgto close the: nozzle opening when desired. Chamber l2 has near ton and hottom two manholes l3 and id through which the filter matcrihlmay he and receptacles, conheat interchangor and valved gas exitare in function to those of Figs. 11 and 21. The

shaft to the work required tube memes there,

is an important function of the apparatus arrangemeut, ermitting adirwhnent or the burden Ira l, 2 and 3; are adapted to function similarly in of cyanide and of reduced metal as byproducts. This dual is carried on simultaneously and the relative proportions of the cyanide and the metal produced by the exof fuel energy can be varied as desired between rather wide High grade producer gas withdrawn through the hush cover outlet is always a third byproduct and most of this is available as surplus gas" not needed to he two integrated sections, hearth-bush and shaft communicating through an unobstructed opening formed in the bush cover. The hot gas outlet in the hash cover can he made of snlficient size to withdraw from the furnace all the surplus gas produced from the air-blast and not needed for work in the shaft. This withdrawn surplus may be over or the hosh gas- In efiect the shaft and the boob gas outlet are regulated ducts Ieadm gas from the hush. In regulating the respective portions of gas passing out through the bash gas outlet and through the shaft to pass out the top of the furnace, the nozzle and valve l8 maintalninga hack pressure in the cyanide condense; may cooperate with the valve in the top gas outlet. Proportioning the gas going through the ratio in accordance with the hearth heatavaih able for completing" the: smelfing'process.

altion, the proportion ofpotash or other soda, etc. charged with the incl is coordinated with the proportion of gas. passed the bosh gas outlet which aiiords outlet for cyanide vapor from the furnace. Such coordination dethe accumulation oi in the furnace and-the nitrogen fixation. An example of the coordinating function-of the hosh gas outlet is shown in a iurnace operation comprising PIG-1 duction. or one gross ton basic pig iron and 6.6 ton slag vfirorn a out 2 ore, one half ton limestone and Wm pound coke carbon, oi? which'fill potmds goes into the Big to give it 4 per cent. carbon content. M will pounds carbon per 'ton his, all gasified in the by the hotblast, less than half is required to generatethc heat needed to heat.the metal and slag'to the reouirsd'tor separation and to burn the limestone. And the CO gas from half the carbon gasified by is more than suflicient to reduce the-ore to metal by exothermic action forming C02. Hence it follows that atv Ieast one half of the carbon [owning with air in the hearth. is available for the purpose of lining blast nitro-. gen in theionn of cyanide vapor. The usual ore. coke, and limestone fed to the blast furnace conpotash and soda equivalent to at least one per cent KCN by weight of the iron produced. The amount of heat required to form cyanide vapor the being that available with ordinary blast temperatures in gasifying' some 5 pounds carbon per pound of nitrogen contained the vapor of potassium or cyanide, it is found that in making basic pig iron as described the furnace can produce as a byproduct at least 800 pounds potassiimr cyanide containing lfill pounds fixed nitrogen per ton me. This is possible by adding alkali to the charge. The cyanide yield can he'morc than 35 per cent by weight of the pig iron. The nitrogen fixed is 10 per cent by weight oi the coke carbon consumed.

In the operation, the bush gas outlet has the iunction of coordinating the withdrawal and re-' covery of cyanide, with the charge of potash or soda in or with the ore and coke and thus of adjusting the burden of ore of alkali. with a given percentage of potash in the charge, such 'for example as the equivalent of one per cent KCN by weight of the pig iron produced, a with drawal through the bosh outlet of one half the gas may remove from the furnace 90* percent or more of the potashinput. This substantially prevents accumulation of potash in the furnace and releases heat to be used for hearth work in smelting ore: the fixation of blast nitrogen being thus reduced to a minimum, so that the ore burden can be greatly increased But by increasing the percentage of potash in the charge. whch is readily done by returning to the furnace potash formed by hydrolysis of cyanide'in chamber 2!.

the yield of cyanide can be greatly increased without decrease of the iron output. Thus the outlet, coordinated with the charge of alkali at the top of the furnace shaft. .Thus, the bosh gas outlet affords means for improving the smelting efllciency of the blast furnace by control of the chemical activity of the blast nitrogen in forming cyanide vapor in the hearth, The outlet of hot cyanide vapor laden gas can be ad'- iusted in coordination with the amount of potash charged to increase the smelting efficiency as desired by limiting'the production of cyanide.

In the operation as described, it becomes possible to supply all needed blast heat b means of the heat interchanger or recuperator transferring sensible heat from bosh gas to the air blast,

after condensation and removal of cyanide. In addition, it is noted that withholding from the shaft of surplus gas formed in the hearth has the result of preventing solution loss of coke; it being now possible to burn with air in the hearth all the carbon charged as fuel. In certain cases it is possible to burn with air excess carbon deposited in reversal of the solution loss reaction, that is, actually more carbon than the amount charged as fuel. This is an added function of the bosh gas outlet running through the bosh top cover.

In thefurnace of Fig. 3, the heavy bosh wall extending to a greater height than the bosh of Fig. 1 or Fig. 2 has the advantage of conserving hearth heat and affording time for completion of smelting work devolving upon the hearth. The

purifying cya- 2,26l,516,. Here the divided furnace is used toproduce'metal ofhigh silicon content with cyanide byproduct and with recovery of coal volatiles in liquid form when desired. What I claim is:

l. A nitrogen-fixing, gas-producing, silicon-reducing hot blast furnace which comprises a bosh and hearth section having air tuyeres and means for blowing a blast of preheated air under pressure and a metal outlet at a level below the air nace being providednear the end of the shaft section remote from the bosh cover, regulated gas outlet means running vertically upward through said bosh cover and adapted to withdraw from the furnace a large regulated fraction of the gas formed by the air blast in the hearth-bosh section, associated means for maintaining a substantial back pressure of gas in said outlet, means connected with said bosh gas outlet for, recovering from the gas condensible gaseous nitrogen compounds formed by the air blast,v connected heat interchanger means for pre-heating the air blast with sensible heat carried out of the furnace in gas withdrawn therefrom through said hot gas outlet and means for regulating the fraction of gas withdrawn.

3. A metallurgical blast furnace improved by having ahearth and bosh of usual construction provided with the conventional air tuyeres and with means for admitting l under pressure through thetuyres to the furnace a preheated air blast and also provided with a refractory roof cover interposed between the hearth-boshand the shaft of the furnace, a shaft through which solid carbonaceous fuel is charged having open communication with the bosh at the top thereof through said roof cover, said communication providing unobstructed passage of both solids and gases a separate hot gas outlet of relatively large size leading from the top of the bosh through said roof cover away from the furnace, adjustable meansassociated with the shaft and hot gas outlet, respectively, for regulating the proportions of gas passed from the bosh through the shaft and withdrawn from the furnace through the hot gas outlet, means associated with the hot gas outlet for separately. disposin of vapors'of saline matter withdrawn from the furnace with the gas, and a heat interchanger preheating the air blast with sensible heat car- "ried out of the furnace through said hot gas outlet.

4. A continuously operated hot blast furnace divided into two integral sections of bosh-hearth and shaft having a roof member covering the furnace bosh-hearth section ofconventional type provided with conventional air tuyres an'd with means for introducing the preheated air blast under substantial positive pressure, a connection through said roof member providing unobstructed passage of solids and gases between said two sections of the furnace, a hot gas outtuyeres, a roof memberforming a top of said seca heat interchangerpreheating the air blast connected'in series to said outlet, a separate shaft section having-open communication through said roof member with the top of said bosh and hearth section and provided with solid fuel charging means and means maintaining the gas pressure and regulating the proportions of gasrespective- 1y passing from the hearth and bosh section through. said gas outlet to said condenser and through said shaft section.

2. A metallurgical blast furnace divided into two integrated inter-communicating sections comprisin hearth-bosh and shaft sections, the latter extending through a refractory cover member over the bosh, conduit means running through said cover providing unobstructed free passage of both solids and gases between said sections, means for charging solids into the furlet running through said roof member and capable of withdrawing from the furnace for outside use a large fraction of the producer gas formed by the air, means for charging solid carbonaceous fuel at the end of the shaft section opposite to the bosh connection, throttling means in said hot gas outlet for maintaining a substan- I tial positive pressure of gas within said bosh, means for recovering nitrogen compounds produced in the furnace and'withdrawn with the gas, and means regulating the relative proportions of bosh gas passing from the bosh through said communicating shaft and through said hot gas outlet, respectively.

' 5. A continuously operated hot blast furnace divided into two integral hearth and shaft sections by a refractory roof'member covering the furnace bosh-hearthsection of conventional type provided with the conventional air'tuyeres and with means for introducing the preheated.air blast under substantial positive pressure, the

shaft section comprising a rotary horizontal kiln having an. open connection with said bosh run-.

' ning through said roof member, and providing unobstructed passage of solids and gases between said two sections of the furnace, a. hot gas outlet running through. said roof member and eapable of withdrawing from the furnace for out--- side use a large fraction of the hot producer gas formed by the air, means connected-with said hot gas outlet for disposing ,of cyanide withdrawn from the furnace with the gas, means for charging-solid carbonaceous fuel at the end of the shaft section opposite to the bosh connection, nozzle means connected with said hot gas outlet for restricting the flow of gas and for maintaining a substantial positive pressure of gas within said bush and means regulating the relative proportions of hot gas passed from the low the air tuyres, a roof member forming a top of said section, a gas outlet for withdrawing from the top of said section a major portion of the gases formed by the air blast, means communicating with said gas outlet for recovering nitrogen compounds produced in the furnace and withdrawn with the gas, a separate shaft sechearth section and provided with solid fuel charging means, and means for separately regulating the gas passing through said shaft section and through said'gas outlet from the hearth and bosh section.

7. A metallurgical; blast furnace-comprising a bush and hearth section having an: tuyre's for admitting a preheated air blast, a roof member covering the bosh, a communicating shaft section separated from said bosh-hearth section by said roof member and delivering-solids into the bosh through said roof, a vertically directed gas outlet provided in said roof, a gas conduit leading gases from said outlet, hot gas filtering means in said conduit, a heat interchanger receiving bosh gases from said -conduit and adapted to recuperate sensible heat therefrom, means for blowing air through the interchanger to carry saidrecuperated-heat in the air admitted to the air tuyeres and means for. regulating the relative proportions of gas passing from the hearth through said-shaft section and through said gas conduit to said heat exchanger, respectively.

RICHARD FRANCHOT. 

